CN1934201B - Active energy ray curable coating composition and molded product - Google Patents
Active energy ray curable coating composition and molded product Download PDFInfo
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- CN1934201B CN1934201B CN2005800094597A CN200580009459A CN1934201B CN 1934201 B CN1934201 B CN 1934201B CN 2005800094597 A CN2005800094597 A CN 2005800094597A CN 200580009459 A CN200580009459 A CN 200580009459A CN 1934201 B CN1934201 B CN 1934201B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D155/00—Coating compositions based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09D123/00 - C09D153/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
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Abstract
An active energy ray-curable coating composition comprising (meth)acryloylated compound mixture (A), the (meth)acryloylated compound mixture containing 22 to 62% of (meth)acryloylated copolymer (A1) obtained by reaction of radically polymerizable monomer (a1) having a specified amount of quaternary ammonium salt group, hydroxylated radically polymerizable monomer (a2) and radically polymerizable monomer (a3) of lactone ring-opening addition structure, and colloidal silica (B). Further, there is provided a molding comprising a coating resulting from curing of the above coating composition. A coating of cured composition exhibiting excellent abrasion resistance, transparency and antistatic property, whose antistatic property deterioration is low even in the storage in high humidity, can be provided.
Description
Technical field
The present invention relates to active energy ray curable coating composition and molding.
Background technology
At present, plastics, for example polycarbonate-based resin, acrylic resins such as polymethylmethacrylate, polyethylene terephthalate, polyester based resins such as polybutylene terephthalate, ABS resin, the MS resin, phenylethylene resin series such as AS resin, the polyvinyl chloride resin, resin base materials such as acetate fiber prime system resin such as triacetyl cellulose, because of its good light weight, workability, shock-resistance etc. are as container, the device panel, wrapping material, various timbering materials, optic disc base board, plastic lens, the base material of indicating meter such as liquid-crystal display and plasma display etc. is used to various uses.
But, because the surface hardness of these plastics is low, so subject to damage.Therefore, the such transparent resin of polycarbonate or polyethylene terephthalate exists because of obvious impaired shortcomings such as the transparency of using the resin script repeatedly and outward appearances, particularly has the use of the plastics in the desired field very difficult to wear resistant.Therefore, with the wear resistant purpose with the surface of giving above-mentioned plastics, dura mater material (coating material) is provided.But the cured layer of dura mater material in the past is because surperficial intrinsic resistance value height easily produces the electrostatic shortcoming so exist.The static that is produced can impel dust etc. to the adhering to of product, so can diminish the attractive in appearance and transparent of product.
Therefore, various dura mater materials with static resistance have been proposed now.For example; as the example of realizing static resistance and wear resistant simultaneously; known have comprise the active energy ray curable coating composition (with reference to patent documentation 1) that intramolecularly has (methyl) acrylic copolymer of quaternary ammonium salt group and (methyl) acryl, comprise the composition (with reference to patent documentation 2) that intramolecularly has the resin compound of betaine structure and free radical reaction unsaturated group.But the cured article of these compositions can't possess enough wear resistants, static resistance and the transparency simultaneously.When particularly under high humidity environment, placing, the tendency that exists static resistance to descend because manifesting the oozing out of material of static resistance.
In addition, when being used for the field of indicating meter or CD, under the situation of the cured layer that is provided with dura mater material with static resistance, in order to weaken the load that cleaning time institute's externally applied forces causes, make cleaning become easy, and in order to prevent that fingerprint from adhering to, in most cases to surperficial oilness and the requirement to some extent of anti-fingerprint tack.
Patent documentation 1: the Japanese Patent spy opens 2002-194250 communique (claim scope)
Patent documentation 2: the Japanese Patent spy opens 2004-43790 communique (claim scope)
The announcement of invention
Problem of the present invention provides can form by the irradiation active energy beam solidifies, have good wear resistant, the transparency and static resistance, even the coating composition of the also less cured article tunicle of the decline of static resistance when particularly under high humidity, placing.In addition, another problem of the present invention provides to form and not only can manifest good wear resistant, static resistance and the transparency, also has the coating composition of the cured article tunicle of surface of good oilness and/or anti-fingerprint tack for a long time.
The invention provides following coating composition and have the molding of the tunicle that its cured article forms.
(1) active energy ray curable coating composition; said composition is characterised in that; the mixture (A) and the colloid silica (B) that comprise compound with (methyl) acryl; 22～62% hydroxyls for the isocyanate group that makes the compound (c) that contains (methyl) acryl and isocyanate group in 1 molecule and polymkeric substance (b) of mixture (A) have carried out the multipolymer (A1) of the structure that addition reaction gets; described polymkeric substance (b) is by comprising the free radical polymerization monomer (a1) with quaternary ammonium salt group; have the free radical polymerization monomer (a2) of hydroxyl and have 1 expression of following formula structure free radical polymerization monomer (a3) free radical polymerization monomer mixture (a) reaction and get; the ratio of monomer (a1) is 20～45 mass parts with respect to total 100 mass parts of monomer mixture (a) and compound (c); 20～85 moles of % of the hydroxyl in the monomer mixture (a) and the isocyanic ester radical reaction of compound (c)
-(C (=O) C
mH
2mO)
n-... formula 1
In the formula 1, m is 3～5 integer, and n is 1～10 integer.
(2) (1) described active energy ray curable coating composition wherein, has the mixture (A) of the compound of (methyl) acryl with respect to 100 mass parts, the conduct that comprises 0.1～500 mass parts forms the colloid silica (B) of branch admittedly.
(3) (1) or (2) described coating composition; wherein; have (methyl) acryl compound mixture (A) 0.01～10% be intramolecularly has position (α) that at least 1 part by the part that is selected from following formula 2～6 expression forms, the position (β) that formed by at least 1 part of the part that is selected from following formula 7～9 expressions reaches (methyl) acryl compound (A2)
-(SiR
1R
2O)
p-... formula 2
-(CF
2CF
2O)
q-... formula 3
-(CF
2CF (CF
3) O)
r-... formula 4
-(CF
2CF
2CF
2O)
s-... formula 5
-(CF
2O)
t-... formula 6
In the formula 2, R
1, R
2Represent in the fluorine-containing alkyl or phenyl of alkyl, carbonatoms 1～8 of carbonatoms 1～8 any independently, p is 1～1000 integer, and in the formula 3～6, q, r, s and t are respectively 1～100 integer,
-R
3-... formula 7
-(CH
2CH
2O)
x-(CH
2CH (CH
3) O)
y-... formula 8
-(C (=O) C
uH
2uO)
z-... formula 9
In the formula 7, R
3Be the alkylidene group of carbonatoms 6～20, in the formula 8, x and y are 0～100 the integer that satisfies 5≤x+y≤100, and in the formula 9, u is 3～5 integer, and z is 1～20 integer.
(4) molding, this molding be characterised in that, on substrate surface, have (1)～(3) in the thickness that forms of the cured article of each described coating composition be the tunicle of 0.1～50 μ m.
The tunicle that the cured article of coating composition of the present invention forms manifests good wear resistant, static resistance and the transparency simultaneously, even the decline of static resistance is also less when particularly placing under high humidity.
In addition, when coating composition contained compound of the present invention (A2), the tunicle that can give cured article formation for a long time was with surface lubrication and/or anti-fingerprint tack.
The best mode that carries out an invention
In this specification sheets, acryl and methacryloyl are referred to as (methyl) acryl, acrylate and methacrylic ester are referred to as (methyl) acrylate, vinylformic acid and methacrylic acid are referred to as (methyl) vinylformic acid.
In the coating composition of the present invention, mixture (A) (below be also referred to as mixture (the A)) expression with compound of (methyl) acryl has the structure of quaternary ammonium salt group, hydroxyl, 1 expression of following formula and the multipolymer (A1) of (methyl) acryl (below be also referred to as multipolymer (A1)) and multipolymer (A1) compound with (methyl) acryl in addition.
22～62% hydroxyls for the isocyanate group that makes the compound (c) that contains (methyl) acryl and isocyanate group in 1 molecule and polymkeric substance (b) of mixture (A) have carried out the multipolymer (A1) of the structure that addition reaction gets, and described polymkeric substance (b) is by comprising free radical polymerization monomer (a1), the free radical polymerization monomer (a2) with hydroxyl with quaternary ammonium salt group and having following formula 1
-(C (=O) C
mH
2mO)
n-... formula 1
(in the formula 1, m is 3～5 integer, and n is 1～10 integer.)
The free radical polymerization monomer mixture (a) of the free radical polymerization monomer (a3) of the structure of expression reacts and gets.
Multipolymer (A1) manifests static resistance because having quaternary ammonium salt group and hydroxyl; because have (methyl) acryl by active energy beam irradiation and with mixture (A) in other compound generation curing reaction, oozing out of multipolymer (A1) is suppressed.
Structure shown in the above-mentioned formula 1 represents that the open loop of lactone adds adult.Multipolymer (A1) is because have a structure shown in the formula 1, and the intermiscibility of other compound in itself and the mixture (A) increases, and the tunicle that is formed by the cured article of coating composition shows the good transparency.Kind to lactone is not particularly limited, and considers from the complexity of its acquisition and the complexity of open loop addition, is preferably 6-caprolactone (m that is equivalent in the formula 1 is 5).In addition, the n in the formula 1 represents the mean polymerisation degree of lactone.If n surpasses 10, then crystallinity increases, and the transparency of the tunicle of cured article formation is descended, so undesirable.N better is below 5.In addition, n is that the transparency of 2 tunicles when above is good especially, so more satisfactory.
The ratio of monomer (a1) is 20～45 mass parts with respect to total 100 mass parts of monomer mixture (a) and compound (c).The ratio of the monomeric unit with quaternary ammonium salt group in this numerical range and the multipolymer (A1) is relevant.Lower limit is preferably more than 23 mass parts, and the upper limit is preferably below 40 mass parts.If less than 20 mass parts, then multipolymer (A1) possibly can't manifest enough static resistances.On the other hand, if surpass 45 mass parts, then the wetting ability of multipolymer (A1) becomes too high, descends with the intermiscibility of other composition of coating composition, and the transparency of cured article can be impaired or bad phenomenon such as cured article albefaction occurs under high humidity.
Multipolymer (A1) is the isocyanic ester radical reaction of 20～85 moles of % of the hydroxyl in the monomer mixture (a) and compound (c) and the multipolymer that obtains.More preferably 30 moles more than the % of the lower limits of this numerical range, particularly preferably 40 moles more than the %, more preferably 80 moles below the % of the upper limits, particularly preferably 75 moles below the %.The amount of (methyl) acryl that is imported in this numerical range and the multipolymer (A1) is relevant with the amount of remaining hydroxyl.If above-mentioned numerical value is high, the amount of (methyl) acryl that promptly is imported into is many, and other composition when then solidifying and in the coating composition fully forms covalent linkage, multipolymer (A1) under high humidity anti-exudative well.If above-mentioned numerical value is low, the amount of (methyl) acryl that promptly is imported into is few, then the anti-exudative decline under the high humidity of multipolymer (A1).On the other hand, under the high situation of above-mentioned numerical value, the quantitative change of clear and definite remaining hydroxyl is few, but the manifesting property decline of the static resistance of multipolymer (A1).Its reason is also indeterminate, may be because the cause that descends as the anionic movability of the counterion of quaternary ammonium salt group along with the decline of hydroxyl concentration.If in above-mentioned numerical range, then anti-exudative the and static resistance of multipolymer (A1) under high humidity is all good.
Multipolymer (A1) can obtain by following 2 kinds of methods that exemplify.
(1) make free radical polymerization monomer mixture (a) reaction of free radical polymerization monomer (a3) that comprises free radical polymerization monomer (a1), free radical polymerization monomer (a2) and have a structure of formula 1 expression obtain polymkeric substance (b), the method that makes the isocyanate group that contains the compound (c) of (methyl) acryl and isocyanate group in the hydroxyl of this polymkeric substance (b) and 1 molecule carry out addition reaction again with hydroxyl with quaternary ammonium salt group.
(2) make free radical polymerization monomer mixture (a) reaction of free radical polymerization monomer (a3) that comprises free radical polymerization monomer with tertiary amine groups (a1 '), has the free radical polymerization monomer (a2) of hydroxyl and have a structure of formula 1 expression obtain polymkeric substance (b '); make the isocyanate group that contains the compound (c) of (methyl) acryl and isocyanate group in the hydroxyl of this polymkeric substance (b ') and 1 molecule carry out addition reaction, the method that makes the alkylating reagent (d) and the tertiary amine groups of this polymkeric substance carry out addition reaction then again.
Free radical polymerization monomer mixture (a) is represented free radical polymerization monomer described later (a1)～(a4) synoptically, and expression has the monomer of free-radical polymerised unsaturated link(age)s such as (methyl) acryl, vinyl, allyl group.
Free radical polymerization monomer (a1) with quaternary ammonium salt group can react in advance by free radical polymerization monomer with tertiary amine groups described later (a1 ') and alkylating reagent (d) and get.Owing to there is the good more tendency of the more little static resistance of alkyl on the nitrogen-atoms, so be preferably with methyl chloride with (methyl) vinylformic acid N the chlorination 2-methacryloxyethyl trimethyl ammonium of N-dimethylamino ethyl ester quaternary ammonium salinization.
Free radical polymerization monomer (a1 ') with tertiary amine groups is (methyl) vinylformic acid and N, the ester of N-dialkyl aminoalkyl alcohol, specifically can exemplify (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N, N-dimethylamino propyl ester, methacrylic acid N, N-diethylamino ethyl ester, methacrylic acid N, N-dibutylamino ethyl ester etc.Owing to there is the good more tendency of the more little static resistance of alkyl on the nitrogen-atoms, thus (methyl) vinylformic acid N particularly preferably, the N-dimethylamino ethyl ester.
Free radical polymerization monomer (a2) with hydroxyl is preferably the free radical polymerization monomer with alcoholic extract hydroxyl group, for example can exemplify (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, (methyl) vinylformic acid 3-chloro-2-hydroxypropyl acrylate etc.
Free radical polymerization monomer (a3) with structure of following formula 1 expression be preferably that lactone carries out opening with above-mentioned monomer (a2) and must monomer.
-(C (=O) C
mH
2mO)
n-... formula 1
(in the formula 1, m is 3～5 integer, and n is 1～10 integer.)
For example, can exemplify make 6-caprolactone and the ethyl ester addition of vinylformic acid 2-hydroxyl and compound.Monomer (a3) is when also having hydroxyl, in this specification sheets by use this monomer (a3), regard as use simultaneously monomer (a2) and monomer (a3) both, the molar weight of the hydroxyl in the monomer mixture (a) has also comprised the molar weight of the hydroxyl of monomer (a3) like this.
Free radical polymerization monomer mixture (a) also can comprise can with other free radical polymerization monomer (a4) of monomer (a1), monomer (a1 '), monomer (a2) and monomer (a3) copolymerization.As other free radical polymerization monomer (a4), can exemplify (methyl) esters of acrylic acid, (methyl) acrylic amide, hydrocarbon system olefines, vinyl ethers, pseudoallyl ethers, allyl ethers, vinyl esters, allyl ester class etc.For example, can exemplify general formula CH
2=C (R
4) COOC
kH
2k+1(R
4Be hydrogen atom or methyl, k is 1～13 integer, C
kH
2k+1Can be that linear chain structure also can be a branched structure) expression (methyl) alkyl acrylate; (methyl) allyl acrylate; (methyl) vinylformic acid benzene methyl; (methyl) vinylformic acid butoxy ethyl ester; (methyl) 2 cyanoethyl acrylate; (methyl) cyclohexyl acrylate; (methyl) vinylformic acid 2,3-dibromo propyl ester; (methyl) vinylformic acid 2-ethoxy ethyl ester; (methyl) vinylformic acid 2-(2-ethoxy ethoxy) ethyl ester; (methyl) 2-EHA; (methyl) glycidyl acrylate; γ-(methyl) acryloxy propyl trimethoxy silicane; (methyl) vinylformic acid 2-methoxyl group ethyl ester; (methyl) acryloyl morpholine; isobornyl acrylate etc.
As the compound (c) that contains (methyl) acryl and isocyanate group in 1 molecule, consider from the complexity that obtains, be preferably isocyanic acid 2-(methyl) acryloxy ethyl ester.In addition, but for example exemplified by acrylic 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxypropyl acrylate, vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, vinylformic acid 4-hydroxy butyl ester, vinylformic acid 3-hydroxypropyl acrylate, caprolactone modification vinylformic acid 2-hydroxyl ethyl ester, phthalic acid 2-acryloxy ethyl-2-hydroxyl ethyl ester, pentaerythritol triacrylate, five vinylformic acid bis(pentaerythritolester)s etc. have isocyanate compounds such as the acrylate of hydroxyl and tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate mol ratio 1: 1 add adult etc.
As alkylating reagent (d), but haloalkanes such as exemplified by methyl chlorine, Butyryl Chloride, monobromomethane, methyl-iodide for example, halogenide such as phenmethyl chlorine, chloracetic acid methyl esters, chloracetic acid ethyl ester, alkyl sodium sulfate such as methyl-sulfate, ethyl sulfate ester, sulphonates such as methyl tosylate, methyl benzenesulfonate etc.
Being aggregated in of free radical polymerization monomer mixture (a) adopts conventional radical polymerization initiator to carry out in the solvent.As this solvent, when the polymerization of the free radical polymerization monomer mixture (a) that comprises free radical polymerization monomer with tertiary amine groups (a1 '), can exemplify aromatic hydrocarbons such as toluene, dimethylbenzene, ester classes such as ethyl acetate, propyl acetate, butylacetate, ketones such as acetone, ethyl methyl ketone, hexone, pimelinketone, ethers such as glycol dimethyl ether, ethylene glycol diethyl ether, diglyme, ether-ether classes such as acetate 2-methoxyl group ethyl ester, acetate 2-ethoxy ethyl ester, acetate 2-butoxy ethyl ester are used after also can mixing mentioned reagent.On the other hand, when the polymerization of the free radical polymerization monomer mixture (a) that comprises free radical polymerization monomer (a1) with quaternary ammonium salt group, because the solvability of monomer (a1) in the above solvent that exemplifies be very low, so preferably make the polar solvent that has active hydrogen in water or methyl alcohol, ethanol, propyl alcohol, the ethylene glycol equimolecular.
Radical polymerization initiator as the polyreaction that is used for free radical polymerization monomer mixture (a), preferably use 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile), 2,2 '-azo two azo-compounds such as (2-methylbutyronitriles), organo-peroxides such as benzoyl peroxide, ditertiary butyl peroxide, cumene hydroperoxide.With respect to the total mole number of free radical polymerization monomer mixture (a), the consumption of polymerization starter is preferably 0.1～20 mole of %, more preferably 1～10 mole of %.
In the polyreaction, can be that purpose is used chain-transfer agent to adjust molecular weight as required.Chain-transfer agent is not particularly limited, and being preferably mercaptan such as sulfur alcohol, spicy thioalcohol, octadecanethiol is mixture.With respect to the total mole number of free radical polymerization monomer mixture (a), the consumption of chain-transfer agent is preferably 0.1～20 mole of %, more preferably 1～10 mole of %.
The reaction of polymkeric substance (b) and compound (c) is that isocyanate group and the reactive with active hydrogen from compound (c) begins, so must not carry out in intramolecularly does not have the solvent of active hydrogen of hydroxyl, carboxyl, amino etc.Make as the free radical polymerization monomer mixture (a) that must composition comprises free radical polymerization monomer with tertiary amine groups (a1 ') and react and the used solvent of polyreaction can be directly adopted in the polymkeric substance that obtains (b ') and the reaction of compound (c).On the other hand, make as after must composition comprising free radical polymerization monomer mixture (a) polymerization of free radical polymerization monomer (a1) with quaternary ammonium salt group, because polymkeric substance (b) has the structure of above-mentioned formula 1 expression, so even the solvability that does not have in the solvent of active hydrogen at intramolecularly also can improve.Therefore, the polar solvent that can have active hydrogen as the intramolecularly that polymer solvent uses reacts with compound (c) after replacing with the solvent that intramolecularly do not have active hydrogen again.
The addition reaction of the isocyanate group of the hydroxyl of polymkeric substance (b) and compound (c) can stir 1～24 hour and finish polymkeric substance (b) and compound (c) between the temperature of room temperature to 60 ℃.To promote addition reaction to carry out is that purpose can be added catalyzer such as dibutyl tin laurate.With the purpose that is polymerized to of (methyl) acryl of preventing compound in this reaction (c), preferably use stoppers such as 2,6 ditertiary butyl p cresol, 4-methoxyphenol.Its consumption is preferably 0.01～2% with respect to reaction mixture, and more preferably 0.05～1.5%.
The tertiary amine groups that makes the polymkeric substance that obtains as free radical polymerization monomer mixture (a) copolymerization that must composition comprises free radical polymerization monomer with tertiary amine groups (a1 ') (b ') and the addition reaction of alkylating reagent (d) can be by adding and the alkylating reagent (d) of tertiary amine groups equimolar amount, between the temperature of room temperature to 60 ℃ to polymkeric substance (b ') and alkylating reagent (d) stirring 1～24 hour and finish.
Molecular weight to multipolymer (A1) is not particularly limited, and the weight-average molecular weight of multipolymer (A1) is preferably 1000～100000, and more preferably 2000～50000.If surpass 100000, then the crystallinity of multipolymer (A1) increases, and the transparency of the tunicle that the cured article of coating composition forms may descend.In addition, if less than 1000 then has easy possibility of oozing out under the high humidity.Weight-average molecular weight among the present invention is a value of utilizing gel permeation chromatography (GPC) to record with polystyrene conversion.
22～62 quality % of mixture (A) are multipolymer (A1).If less than 22%, then the static resistance of the tunicle of the cured article of coating composition formation is poor.If surpass 62%, then the wear resistant of the tunicle of the cured article of coating composition formation is poor, oozing out of multipolymer (A1) can occur under the high humidity.
Have in the mixture (A) of compound of (methyl) acryl and preferably contain compound (A2).The position (β) that the intramolecularly of compound (A2) has position (α) that at least 1 part by the part that is selected from following formula 2～6 expression forms, formed by at least 1 part of the part that is selected from following formula 7～9 expressions reaches (methyl) acryl.
-(SiR
1R
2O)
p-... formula 2
-(CF
2CF
2O)
q-... formula 3
-(CF
2CF (CF
3) O)
r-... formula 4
-(CF
2CF
2CF
2O)
s-... formula 5
-(CF
2O)
t-... formula 6
(in the formula 2, R
1, R
2Represent in the fluorine-containing alkyl or phenyl of alkyl, carbonatoms 1～8 of carbonatoms 1～8 any independently, p is 1～1000 integer, and in the formula 3～6, q, r, s and t are respectively 1～100 integer.)
-R
3-... formula 7
-(CH
2CH
2O)
x-(CH
2CH (CH
3) O)
y-... formula 8
-(C (=O) C
uH
2uO)
z-... formula 9
(in the formula 7, R
3Be the alkylidene group of carbonatoms 6～20, in the formula 8, x and y are 0～100 the integer that satisfies 5≤x+y≤100, and in the formula 9, u is 3～5 integer, and z is 1～20 integer.)
Compound (A2) is by the position (α) that the part with following formula 2 expression forms, and can give tunicle that the cured article of coating composition forms with surface lubrication.In the following formula 2, R
1, R
2Each siloxane unit can be the same or different.As the part of formula 2 expressions, be preferably polydimethylsiloxane unit, PSI unit, poly-diphenyl siloxane unit, R
1And/or R
2Be R
fCH
2CH
2CH
2-(R
fBe Polyfluoroalkyl) poly-fluoroalkyl siloxane unit etc.R
fThe group that the hydrogen atom more than 2 that base is meant alkyl has been replaced by fluorine atom.In the formula 2, p is 1～1000, is preferably 1～500.In this scope, the surface lubrication of the tunicle that is formed by cured article is good.
Compound (A2) is by having at least 1 position (α) that part forms of the part that is selected from following formula 3～6 expression, can give tunicle that the cured article of coating composition forms with surface lubrication and/or anti-fingerprint tack.In the following formula 3～6, p, q, r and s were respectively 1～4 o'clock, helped manifesting anti-fingerprint tack, were 5～100 o'clock, manifested when can expect surface lubrication and anti-fingerprint tack.
At least 1 position (β) that part forms of the part of compound (A2) by having the formula of being selected from 7～9 expression, have manifest with mixture (A) in the performance of intermiscibility of other compound.
The part of following formula 7 expressions is alkylidene groups of the carbonatoms 6～20 of linear chain structure or branched structure.If carbonatoms is in this scope, then the intermiscibility of other compound in compound (A2) and the mixture (A) is more satisfactory, and the crystallinity of this group can be not too high, and the transparency of the tunicle that is formed by cured article is just fine like this.
The segmented copolymer of random copolymers, oxyethane and the propylene oxide of part representative ring oxidative ethane shown in the following formula 8 and propylene oxide, the homopolymer of oxyethane, the homopolymer of propylene oxide.X, the y of expression mean polymerisation degree is 0～100 the integer that satisfies 5≤x+y≤100.X, y better are 0～80 the integers that satisfies 5≤x+y≤80.If x, y are in this scope, then the intermiscibility of other compound in compound (A2) and the mixture (A) is more satisfactory, and the transparency of the tunicle that is formed by cured article well.If x+y surpasses 100, then because the intermiscibility of other compound in compound (A2) and the mixture (A) is too high, so the difficult formation of film coated surface segregation, the tunicle that is formed by cured article can't fully show surface lubrication and/or anti-fingerprint tack.On the other hand, if x+y less than 5, then the intermiscibility of other compound in compound (A2) and the mixture (A) descends, and diminishes the transparency of the tunicle of cured article formation.
Part shown in the following formula 9 represents that the open loop of lactone adds adult.The z of expression mean polymerisation degree is 1～20 integer.If z is in this scope, then the crystallinity of position (β) is suppressed, and the transparency of the tunicle that is formed by cured article is good.
Because compound (A2) has (methyl) acryl, thus utilize the irradiation of active energy beam can cause curing reaction, with other composition formation covalent linkage of coating composition.Take this just the be fixed surface of the tunicle that the cured article that is present in coating composition forms of compound (A2), compound (A2) just can not waved diffusing from the surface of tunicle like this.Therefore, the surface of the tunicle of cured article formation can manifest surface lubrication and/or anti-fingerprint tack for a long time.
Combining form to the position (α) in the compound (A2), position (β) and (methyl) acryl is not particularly limited.Combining form as each position in the compound (A2) specifically can exemplify following example.
(1) straight chain type.Position (α), position (β) and (methyl) acryl are with the connected type of linearity.For example, can exemplify following compound.
Straight chain type
1：R
4(SiR
1R
2O)
p-SiR
1R
2CH
2CH
2CH
2O-B-(CH
2CH
2O)
X-(CH
2CH(CH
3)O)
Y-A
2：R
5(SiR
1R
2O)
p-SiR
1R
2CH
2CH
2CH
2O-B-(C(＝O)C
UH
2UO)
Z-A
3：R
fO-(CF
2CF
2O)
q-CF
2CH
2O-B-(CH
2CH
2O)
X-(CH
2CH(CH
3)O)
Y-A
4：R
fO-(CF
2CF
2O)
q-CF
2CH
2O-B-(C(＝O)C
UH
2UO)
Z-A
5：R
fO-(CF
2CF
2O)
q-(CF
2O)
t-CF
2CH
2O-B-(CH
2CH
2O)
X-(CH
2CH(CH
3)O)
Y-A
6：R
fO-(CF
2CF
2O)
q-(CF
2O)
t-CF
2CH
2O-B-(C(＝O)C
UH
2UO)
Z-A
7：R
fO-(CF(CF
3)CF
2O)
r-CF(CF
3)CH
2O-B-(CH
2CH
2O)
X-(CH
2CH(CH
3)O)
Y-A
8：R
fO-(CF(CF
3)CF
2O)
r-CF(CF
3)CH
2O-B-(C(＝O)C
UH
2UO)
Z-A
9：R
fO-(CF
2CF
2CF
2O)
s-CF
2CF
2CH
2O-B-(CH
2CH
2O)
X-(CH
2CH(CH
3)O)
Y-A
10：R
fO-(CF
2CF
2CF
2O)
s-CF
2CF
2CH
2O-B-(C(＝O)C
UH
2UO)
Z-A
In the following formula, A:-CONH-CH
2CH
2OCOC (R
4)=CH
2(R
4For-H or-CH
3), B: singly-bound ,-CH
2CH
2O-,-CONH-C
6H
4-CH
2-C
6H
4-NHCOO-,-CONH-CH
2CH
2CH
2CH
2CH
2
CH
2-NHCOO-,-CONH-C
6H
3(CH
3)-NHCOO-,-CONH-C
10H
6-NHCOO-,-CO-C
6H
4-COO-,-CO-C
iH
2i+1-COO-(i is 0～10 integer), R
4: hydrogen atom or methyl, R
5: the alkyl of carbonatoms 1～8 (can contain etheric oxygen atom), R
f: carbonatoms 1～16 contain fluoroalkyl (can contain etheric oxygen atom), R
1, R
2, p, q, r, s, t, u, x, y and z as previously mentioned ,-(CF
2CF
2O)-unit and-(CF
2O)-unitary arrangement mode can be that block-wise also can be random shape.
As the starting compound that forms position (α), can exemplify the compound that the end with position (α) has changed hydroxyl into, for example, the end that better can exemplify polymkeric substance such as polydimethylsiloxane, polyhexafluoropropylene oxide, poly-ptfe ring oxidative ethane has changed the compound of hydroxyl etc. into.
Make monomer such as oxyethane, propylene oxide, lactone and above-mentioned end change hydroxyl polymeric in the compound of hydroxyl into position (α), can with position (α) in abutting connection with constructing position (β).Perhaps polymkeric substance such as polyoxyethylene glycol, polypropylene glycol with 2 functionality isocyanic ester by amino-formate bond also can be at the position (α) connecting portion (β).
In the aforesaid operations, the end of position (β) is a hydroxyl.As the method that imports (methyl) acryl therein; can exemplify the method that usefulness (methyl) vinylformic acid, (methyl) acrylate chloride etc. import by ester bond; method with isocyanic acid 2-(methyl) acryloxy ethyl ester imports by amino-formate bond imports the method for (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester etc. etc. via amino-formate bond by 2 functionality isocyanic ester.
In addition; use the polymkeric substance of terminal quilt (methyl) acryl modification of polymkeric substance such as polyoxyethylene glycol, polypropylene glycol in addition; between the terminal hydroxyl of itself and position (α); with formation amino-formate bonds such as 2 functionality isocyanic ester, take this method that position (β) and (methyl) acryl is connected with position (α) adjacency.
(2) copoly type.Preparation has the free-radical polymerised macromonomer at position (α) and has the free-radical polymerised macromonomer at position (β), make these macromonomer copolymerization after, import the type of (methyl) acryl.For example can exemplify following compound.
Copoly type
[G1]：R
5(SiR
1R
2O)
p-SiR
1R
2CH
2CH
2CH
2O-
R
fO-(CF
2CF
2O)
q-CF
2CH
2O-CONH-CH
2CH
2O-、
R
fO-(CF
2CF
2O)
q-(CF
2O)
t-CF
2CH
2O-CONH-CH
2CH
2O-、
R
fO-(CF(CF
3)CF
2O)
r-CF(CF
3)CH
2O-CONH-CH
2CH
2O-、
R
fO-(CF
2CF
2CF
2O)
s-CF
2CF
2CH
2O-CONH-CH
2CH
2O-
[G2]：CH
2＝C(R
4)COOCH
2CH
2-NHCOO-(CH
2CH
2O)
x-(CH
2CH(CH
3)O)
y-、
CH
2＝C(R
4)COOCH
2CH
2-NHCOO-(C(＝O)C
uH
2uO)
z-CH
2CH
2O-、
In the following formula, g1 is 1～20, and g2 is 1～20, R
f, R
1, R
2, R
4, R
5, p, q, r, s, t, u, x, y and z as previously mentioned.
As macromonomer with position (α), for example can exemplify of polymkeric substance such as polydimethylsiloxane, polyhexafluoropropylene oxide, poly-ptfe ring oxidative ethane terminal by the modification of (methyl) acryl compound etc.
As macromonomer with position (β), the open loop that for example can exemplify (methyl) acrylic acid alkyl ester, polyoxyethylene glycol, polypropylene glycol, lactone add of polymkeric substance such as adult terminal by the modification of (methyl) acryl compound etc.
(methyl) acryl can import its end after above-mentioned macromonomer copolymerization.For example, at the terminal hydroxyl of the multipolymer of above-mentioned macromonomer, the method that imports by ester bond with (methyl) vinylformic acid, (methyl) acrylate chloride etc.; With the method for isocyanic acid 2-(methyl) acryloxy ethyl ester by the amino-formate bond importing.
Compound (A2) is preferably 0.01～10 quality % of the mixture (A) of the compound with (methyl) acryl, more preferably 0.1～5 quality %.If in this scope, when then coating composition being coated substrate surface, can not diminish the transparency of filming before solidifying, compound (A2) is in the film coated surface segregation.Therefore, the transparency of the tunicle after the curing can not be affected, and the surface lubrication on this tunicle surface and/or anti-fingerprint tack are good.In addition, if in this scope, then the solidified nature of coating composition can not descend, and compound (A2) is fixed and is present in the tunicle surface when solidifying, so this tunicle surface can manifest surface of good oilness and/or anti-fingerprint tack for a long time.
Have in the mixture (A) of compound of (methyl) acryl; as multipolymer (A1), compound (A2) compound in addition with (methyl) acryl; because the wear resistant of the tunicle that the cured article of coating composition forms is good, so be preferably the compound (A3) (below be also referred to as compound (A3)) of (methyl) acryl that has in 1 molecule more than 2.
Compound (A3) better is to have 2～50 (methyl) acryls, is more preferably to have 3～30 (methyl) acryls.
As compound (A3), for example can exemplify the acroleic acid polyurethane as the resultant of reaction of tetramethylolmethane or its polymer poly tetramethylolmethane, polyisocyanates and (methyl) vinylformic acid hydroxyl alkane ester, it is to have (methyl) acryl more than 2, be more preferably the multi-functional compounds with 4～20 (methyl) acryls; Perhaps as the acroleic acid polyurethane of the resultant of reaction of poly-(methyl) acrylate of the hydroxyl of tetramethylolmethane or polypentaerythritol and polyisocyanates, it is to have (methyl) acryl more than 2, be more preferably the multi-functional compounds with 4～20 (methyl) acryls.
In addition, can exemplify poly-(methyl) acrylate of poly-(methyl) acrylate of tetramethylolmethane system or isocyanuric acid ester system.Poly-(methyl) acrylate of tetramethylolmethane system is meant tetramethylolmethane or polypentaerythritol and (methyl) acrylic acid polyester, is preferably to have 4～20 (methyl) acryls.Specifically be meant trimethylolpropane tris (methyl) acrylate, three (methyl) vinylformic acid pentaerythritol ester, four (methyl) vinylformic acid pentaerythritol ester, six (methyl) vinylformic acid bis(pentaerythritolester), five (methyl) vinylformic acid bis(pentaerythritolester).Poly-(methyl) acrylate of isocyanuric acid ester system is meant isocyanuric acid three (hydroxyalkyl) ester or isocyanuric acid three (hydroxyalkyl) ester 1 mole compound and (methyl) acrylic acid polyester of obtaining with 1～6 mole caprolactone or alkylene oxide addition, is preferably to have 2～3 (methyl) acryls.
Have in the mixture (A) of compound of (methyl) acryl and can comprise the compound (A4) that has 1 (methyl) acryl in 1 molecule.As compound (A4), can exemplify (methyl) esters of acrylic acids such as (methyl) alkyl acrylate, (methyl) allyl acrylate.
Coating composition of the present invention comprises colloid silica (B).Colloid silica (B) is to be colloidal dispersive silicon-dioxide ultra micron in dispersion medium.Median size to the silicon dioxide granule of colloid silica (B) is not particularly limited, but for the high transparent that makes the tunicle that cured article forms manifests, is preferably 1～200nm, more preferably 1～50nm.
As colloid silica, can use dispersive colloid silica in following dispersion medium.Specifically can exemplify water, methyl alcohol, ethanol, Virahol, propyl carbinol, ethylene glycol, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, propylene glycol methyl ether acetate, N,N-DIMETHYLACETAMIDE, toluene, dimethylbenzene, methyl acetate, ethyl acetate, butylacetate, pentyl acetate, acetone etc.Water, lower alcohols, ester class, cellosolve class etc. are owing to have to a certain degree high polarity, thus easily guarantee the dispersion stabilization of colloidal sol, more satisfactory.
As colloid silica (B), for its dispersion stabilization is improved, the modification colloid silica that also can use particle surface to modify through the hydrolyzate of water-disintegrable silane compound, here, " be hydrolyzed thing modify " is meant that part or all the hydrolyzate of silanol group and silane compound on the surface of colloid silica particle passes through physics or chemical mode bonded state, takes this surface property and obtains modification.In addition, the silicon dioxide granule that also comprises the group that similarly is combined with the condensation reaction of having carried out hydrolyzate.This finishing can be by in the presence of the colloid silica particle, carrying out silane compound hydrolization group part or all hydrolysis or it is hydrolyzed and condensation reaction and easily implementing.
As water-disintegrable silane compound, be preferably the silane compound that hydrolization groups such as the organic group of functional groups such as having (methyl) acryl, amino, epoxy group(ing), sulfydryl and alkoxyl group and/or hydroxyl and Siliciumatom combine.For example can exemplify 3-(methyl) acryloxy propyl trimethoxy silicane, 2-(methyl) acryloxy ethyl trimethoxy silane, 3-(methyl) acryloxy propyl-triethoxysilicane, 2-(methyl) acryloxy ethyl triethoxysilane, the 3-aminopropyltriethoxywerene werene, the 3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, the 3-glycidoxypropyltrime,hoxysilane, 3-sulfydryl propyl trimethoxy silicane etc.
With respect to mixture (A) 100 mass parts of the compound with (methyl) acryl, the conduct that better contains 0.1～500 mass parts forms the colloid silica (B) of branch admittedly.More preferably 0.1～300 mass parts, particularly preferably 10～200 mass parts.If in this scope, the tunicle that then solidify to form manifests enough wear resistants, be difficult for to take place muddyly, and external force is difficult for causing and breaks.
Mixture (A) 100 mass parts with respect to the compound with (methyl) acryl better contain 0.1～20 mass parts active energy beam polymerization starter (C) in the coating composition, be more preferably and contain 0.2～10 mass parts.If the amount of active energy beam polymerization starter (C) is in above-mentioned scope, then solidified nature is enough, and active energy beam polymerization starters (C) whole during curing will decompose, so very desirable.
Active energy beam polymerization starter (C) comprises various known Photoepolymerizationinitiater initiaters.Concrete example have aryl ketones be Photoepolymerizationinitiater initiater (for example; acetophenones, benzophenone, alkylamino benzophenone, benzil class, bitter almond oil camphor class, benzoin ethers, benzil dimethyl ketal class, benzoylbenzoic acid ester class, α-acyl group oxime ester class etc.); sulfur-bearing be Photoepolymerizationinitiater initiater (for example; thioether class, thioxanthene ketone etc.); acylphosphine oxide class (for example, acyl group diaryl phosphine oxide etc.) and other Photoepolymerizationinitiater initiater.This Photoepolymerizationinitiater initiater also can more than 2 kinds and be used.In addition, Photoepolymerizationinitiater initiater can be used in combination with photosensitizerss such as amines.
Coating composition of the present invention can comprise the functional admixture more than a kind that is selected from organic solvent, UV light absorber, photostabilizer, antioxidant, hot stopper, flow agent, defoamer, tackifier, anti-sedimentation agent, pigment (organic coloring pigment, mineral dye), illuminating colour, infrared absorbent, white dyes, dispersion agent, stain control agent, coupling agent as required.
Coating composition of the present invention is coated with methods such as method, intaglio plate coating method, rolling method, scraper coating method, airblade coating method and coats base material by dip coating, spin-coating method, flow coat method, spraying method, rod, when containing the composition of organic solvent, dry back irradiation active energy beam makes its curing.
As active energy beam, better can exemplify ultraviolet ray, electron rays, X ray, radioactive rays and high-frequency ray etc., economical especially is the ultraviolet ray with wavelength of 180～500nm.
The thickness of the tunicle that the cured article of coating composition forms can adopt all thickness as required.Usually be preferably the thick tunicle of 0.1～50 μ m, more preferably the thickness of 0.2～20 μ m, the particularly preferably thickness of 0.3～10 μ m.In this scope, wear resistant is enough by film thickness, and the curing in tunicle deep is also abundant, and is therefore more satisfactory.
Formed the material of the base material of tunicle as cured article, can exemplify as plastics such as aromatic polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polymethylmethacrylate, PMAm, polystyrene, polyvinyl chloride, unsaturated polyester, polyolefine, ABS resin, AS resin, MS (methyl methacrylate vinylbenzene) resins by coating composition of the present invention.Tunicle can directly be present on the base material, base material and also can be had the middle layer by intermembranous.
Embodiment
Below, the present invention will be described based on embodiment (example 1～6) and comparative example (example 7～11), but the present invention is not limited to this.Number-average molecular weight is to be the value that standard substance records with the polystyrene by gel permeation chromatography.
(synthesis example 1)
Compound (A1-1)
In 4 mouthfuls of flasks of the 1L that stirrer and prolong are housed, pack 2 into, behind 2 '-Diisopropyl azodicarboxylate (2.67g) and the spicy thioalcohol (2.38g), add methyl alcohol (189g) and dissolve.Then, compound (the ダ イ セ Le chemical industry Co., Ltd. system that adds chlorination 2-methacryloxyethyl trimethyl ammonium (30.00g) and 1 mol propylene acid 2-hydroxyl ethyl ester and average 2 moles of 6-caprolactone additions and obtain, trade(brand)name " プ ラ Network セ Le FA2D ") (64.74g), in 65 ℃ of heated and stirred 6 hours.
Then, replace prolong, add pimelinketone (184.85g),, the whole steaming of the methyl alcohol in the system removed in 100 ℃ of heating with fractionating tube.Then, reaction soln is cooled to room temperature, add 2 again, 6-ditertbutylparacresol (2.13g) and dibutyl tin laurate (0.31g), add isocyanic acid 2-methacryloxy ethyl ester (21.00g) at last, stirred 12 hours under the room temperature, obtain the pimelinketone solution (40% solid formation divided) of the multipolymer (A1-1) of water white weight-average molecular weight 7000.
(synthesis example 2～7)
Compound (A1-2～7)
Except the kind of the monomer in the synthesis method of compound (A1-1), solvent, additive etc. and consumption being become the kind and amount of following table 1 record, make compound (A1-2～7) with the same operation of the synthesis method of compound (A1-1).In the table 1, プ ラ Network セ Le FA1 is the 6-caprolactone addition of 1 mole vinylformic acid 2-hydroxyl ethyl ester and 1 mole and the compound (ダ イ セ Le chemical industry Co., Ltd. system, trade(brand)name " プ ラ Network セ Le FA1 ") that obtains.
(synthesis example 8)
Compound (A1-8)
In 4 mouthfuls of flasks of the 1L that stirrer and prolong are housed, pack 2 into, behind 2 '-Diisopropyl azodicarboxylate (4.11g) and the spicy thioalcohol (3.66g), add pimelinketone (270g) and dissolve.Then, add methacrylic acid N, N-dimethylamino ethyl ester (35.10g) and 1 mol propylene acid 2-hydroxyl ethyl ester and average 2 moles of 6-caprolactone additions and compound (ダ イ セ Le chemical industry Co., Ltd. system of obtaining, trade(brand)name " プ ラ Network セ Le FA2D ") (99.73g), in 80 ℃ of heated and stirred 6 hours.
Then, reaction soln is cooled to room temperature, adds 2,6 ditertiary butyl p cresol (1.80g) and dibutyl tin laurate (0.35g), add isocyanic acid 2-methacryloxy ethyl ester (23.72g) at last, stirred 12 hours under the room temperature.Then, add methyl chloroacetate (24.16g), stirred 4 hours in 60 ℃, obtain the pimelinketone solution (42% solid formation divided) of the multipolymer (A1-8) of orange-yellow transparent weight-average molecular weight 8000.
(synthesis example 9)
Multipolymer does not possess the example of structure shown in the following formula 1
In 4 mouthfuls of flasks of the 1L that stirrer and prolong are housed, pack 2 into, behind 2 '-Diisopropyl azodicarboxylate (1.64g) and the spicy thioalcohol (1.46g), add methyl alcohol (288g) and dissolve.Then, add chlorination 2-methacryloxyethyl trimethyl ammonium (41.50g), methacrylic acid 2-hydroxyl ethyl ester (26.02g) and isobornyl acrylate (124.80g), in 65 ℃ of heated and stirred 6 hours.Then, methyl alcohol is removed from the reaction soln steaming, carry out vacuum-drying in 12 hours in 70 ℃.Trial is dissolved in the various organic solvents that do not have active hydrogen with the polymkeric substance of gained solid state, but does not all dissolve, and can't carry out the methacrylic acidylate modified-reaction of multipolymer.
Table 1 is depicted as the simple scenario of the compound of compound (A1-1～8).
(synthesis example 10)
Colloid silica (B-1)
At 2-propyl alcohol decentralized colloid silica (dioxide-containing silica 30%, median size 11nm) adds 3-sulfydryl propyl trimethoxy silicane (2.5 mass parts) in (100 mass parts), in 50 ℃ stir 3 hours after, carry out slaking in 12 hours under the room temperature, obtain the dispersion liquid (dividing 31.7%) that the surface has the colloid silica (B-1) of the hydrolytic condensate of the silane compound that contains sulfydryl Gu form.
(synthesis example 11)
Colloid silica (B-2)
At 2-propyl alcohol decentralized colloid silica (dioxide-containing silica 30%, median size 11nm) adds 3-methacryloxypropyl trimethoxy silane (5.0 mass parts) in (100 mass parts), in 50 ℃ stir 3 hours after, carry out slaking in 12 hours under the room temperature, obtain the dispersion liquid (dividing 33.3%) that the surface has the colloid silica (B-2) of the hydrolytic condensate of the silane compound that contains sulfydryl Gu form.
(synthesis example 12)
Compound (A2-1) (giving the compound of surface lubrication)
Pack in 4 mouthfuls of flasks of the 300mL that stirrer and prolong are housed four titanium isobutoxides (80mg), an end have dimethyl silicone oil (Shin-Etsu Chemial Co., Ltd's system of hydroxyl, trade(brand)name " X-22-170BX ", hydroxyl value l8.5) (100g) and 6-caprolactone (25g), stirred 5 hours in 150 ℃, obtained in a terminal open loop addition of dimethyl silicone oil the white waxy compound of 6-caprolactone.The mean polymerisation degree of caprolactone is 6.6.
The gained compound is cooled to room temperature; add butylacetate (50g) and 2; 6-ditertbutylparacresol (250mg); stir after 30 minutes; add isocyanic acid 2-methacryloxy ethyl ester (5.05g); restir is 24 hours under the room temperature, obtains the butylacetate solution (dividing 72% Gu form) of the compound (A2-1) of terminal process methacryloyl modification.Number-average molecular weight about 3750.
(synthesis example 13)
Compound (A2-2) (giving the compound of surface lubrication and anti-fingerprint tack)
Below, tetramethylsilane is designated as TMS, CClF
2CF
2CHClF is designated as R-225, CCl
2FCClF
2Be designated as R-113.
Poly glycol monomethyl ether (the CH that (operation 1) packs into commercially available in the flask of the inner capacities 200mL that possesses thermometer, stirrer, return line and thermoswitch
3O (CH
2CH
2O)
Q+lH,
(mean value)) (25.0g), R-225 (20.0g), Sodium Fluoride (1.2g) and pyridine (1.6g), vigorous stirring when remaining interior temperature below 10 ℃ makes the nitrogen bubbling.Then, when remaining interior temperature below 5 ℃ with dripping FCOCF (CF in 3 hours
3) OCF
2CF (CF
3) OCF
2CF
2CF
3(46.6g).Then, in 50 ℃ of stirrings 12 hours, obtained thick liquid in 24 hours in stirring at room again.The thick liquid of filtration under diminished pressure gained carries out 12 hour drying to filtrate with the drying under reduced pressure machine under 50 ℃, the condition of 666.5Pa.The thick liquid of gained is dissolved in R-225 (100mL), uses saturated sodium bicarbonate aqueous solution (1000mL) washing 3 times again, reclaim organic phase.In the organic phase that reclaims, add sal epsom (1.0g), stirred 12 hours.Remove sal epsom by pressure filtration, steam with vaporizer and remove R-225, obtain to be aqueous compound (56.1g) under the room temperature.
1H-NMR,
19The result that F-NMR analyzes is that the affirmation resulting polymers is CH
3O (CH
2CH
2O)
Q+1COCF (CF
3) OCF
2CF (CF
3) OCF
2CF
2CF
3The compound of (q as previously mentioned) expression.
(operation 2) R-113 (1560g) that packs in the anti-corrosion Langaloy system reactor of the haas troy of inner capacities 3L stirs, and temperature is remained 25 ℃.In the series connection of the pneumatic outlet of reactor the condenser that the particles filled layer of condenser, NaF that temperature remains 20 ℃ and temperature remain-20 ℃ is set.Also be provided with the liquid foldback pipeline that the condenser agglutinative liquid that will be remained-20 ℃ by temperature is returned to reactor.Be blown into nitrogen after 1 hour, being blown into through nitrogen dilution with the flow of 24.8L/h is 10% fluorine gas (hereinafter referred to as " 10% fluorine gas ") 1 hour.
Resultant (27.5g) with injection process 1 acquisition in 30 hours when then, being blown into 10% fluorine gas with same flow is dissolved in R-113 (1350g) and the solution of acquisition.
Then, interior temperature is changed to 40 ℃, when being blown into 10% fluorine gas with same flow, the 6.7%R-113 solution (12mL) of the resultant that injection process 1 obtains.Then, inject the R-113 solution (6mL) that has dissolved 1% benzene.After being blown into 1 hour 10% fluorine gas with same flow again, be blown into 1 hour nitrogen.
Reaction finishes the back drying under reduced pressure, in 60 ℃ steamed with 6 hours desolventize after, obtain to be under the room temperature resultant (45.4g) of liquid.The result that NMR analyzes is to confirm with CF
3O (CF
2CF
2O)
Q+1COCF (CF
3) O
CF
2CF (CF
3) OCF
2CF
2CF
3The compound of expression is main resultant.
After (operation 3) fully replaces the round-bottomed flask of the 300mL that has dropped into stirrer with nitrogen, methyl alcohol (36.0g), Sodium Fluoride (5.6g) and R-225 (50.0g) pack into, after dripping the resultant (43.5g) of operation 2 acquisitions, vigorous stirring when room temperature is carried out bubbling.The outlet of round-bottomed flask is sealed by nitrogen is airtight.
After 8 hours, vacuum pump is set on prolong, internal system is remained decompression state, steam and remove superfluous methyl alcohol and byproduct of reaction.After 24 hours, obtain to be under the room temperature resultant (26.8g) of liquid.The result that NMR analyzes is to confirm with CF
3O (CF
2CF
2O)
qCF
2COOCH
3The compound of expression is main resultant.
(operation 4) fully replaces the round-bottomed flask of the 300mL that has dropped into stirrer with nitrogen.Then, add 2-propyl alcohol (30.0g), R-225 (50.0g) and Sodium Borohydride (4.1g), the resultant (26.2g) with R-225 (30.0g) dilution operation 3 obtains drips gained solution, vigorous stirring under the room temperature.The outlet of round-bottomed flask is sealed by nitrogen is airtight.
After 8 hours, connect vacuum pump on prolong, internal system is remained decompression state, steaming desolventizes.After 24 hours, move to the round-bottomed flask of 1L, drop into R-225 (100g), drip 0.2 mol aqueous hydrochloric acid (500g) in the time of stirring.After being added dropwise to complete, keep 6 hours stirring.Organic phase reclaims organic phase with distilled water (500g) washing 3 times.Then, in the organic phase that reclaims, add sal epsom (1.0g), stirred 12 hours.Then, carry out pressure filtration, remove sal epsom, steam with vaporizer and remove R-225, obtain to be under the room temperature material (24.8g) of liquid.The result that NMR analyzes is to confirm with CF
3O (CF
2CF
2O)
qCF
2CH
2The compound that OH represents is main resultant.
(operation 5) in 4 mouthfuls of flasks of the 200mL that agitator and prolong are housed, pack into four titanium isobutoxides (16mg), CF
3O (CF
2CF
2O)
qCF
2CH
2OH (20g) and 6-caprolactone (5g) in 150 ℃ of heating 5 hours, obtain CF
3O (CF
2CF
2O)
qCF
2CH
2The terminal open loop addition of OH the white waxy compound of 6-caprolactone.Molecular weight is 1250, and the aggregate number of caprolactone is about 2.2.
Then, add 1, two (trifluoromethyl) benzene (12g) of 3-and 2,6 ditertiary butyl p cresol (12mg) stirred after 30 minutes, added isocyanic acid 2-methacryloxy ethyl ester (3.1g), and restir is 24 hours under the room temperature, and reaction is finished.Then, decompression removes as 1 of solvent in 40 ℃ of steamings down, and two (trifluoromethyl) benzene of 3-obtain the terminal compound of modifying through methacryloyl (A2-2).Molecular weight is 1400.
(synthesis example 14)
Compound (A2-3) (giving the compound of anti-fingerprint tack)
According to the method same, use CH with synthesis example 13
3O (CH
2CH
2O)
Q+1H (q=2.3 (mean value)) obtains CF
3O (CF
2CF
2O)
qCF
2CH
2OH.
Four titanium isobutoxides (80mg), CF pack in 4 mouthfuls of flasks of the 300mL that stirrer and prolong are housed
3O (CF
2CF
2O)
qCF
2CH
2OH (100g) and 6-caprolactone (25g) in 150 ℃ of heating 5 hours, obtain CF
3O (CF
2CF
2O)
qCF
2CH
2The terminal open loop addition of OH the white waxy compound of 6-caprolactone.Molecular weight is 580, and the aggregate number of caprolactone is about 1.0.
The gained compound is cooled to room temperature; add butylacetate (56g) and 2; 6-ditertbutylparacresol (60mg); stir after 30 minutes; add isocyanic acid 2-methacryloxy ethyl ester (6.0g); restir is 24 hours under the room temperature, obtains the butylacetate solution (dividing 70% Gu form) of the compound (A2-3) of terminal process methacryloyl modification.Molecular weight is 630.
[example 1]
In 4 mouthfuls of flasks of the 300mL that stirrer and prolong are housed, pack into the solution (0.20g) of 1-hydroxy-cyclohexyl phenyl ketone (2.68g), hydroquinone monomethyl ether (0.83g), compound (A2-1) and the solution (0.20g) of compound (A2-3), the dispersion liquid (76.38g) that adds colloid silica (B-2) more at leisure, normal temperature and shading state stir 1 hour homogenizing down.Then, add the solution (30.88g) of compound (A1-1) when stirring, add pimelinketone (20.14g) and 2-propyl alcohol (27.72g) again, normal temperature and shading state stir 1 hour homogenizing down.Then, add pentaerythritol triacrylate (8.24g) and six vinylformic acid bis(pentaerythritolester)s (32.94g), normal temperature and shading state stir down and obtained coating composition (dividing 42% Gu form) in 1 hour.
At base material (the transparent aromatic polycarbonate resin film-making material of thick 3mm, the surface of 100mm * 100mm) with spinner coating (2000rpm * 10 second) gained coating composition after, it is kept making its drying in 1 minute in 90 ℃ recirculation furnace, and formation is filmed.Then, with high-pressure mercury light irradiation 1000mJ/cm
2The ultraviolet ray of (the ultraviolet accumulated energy of wavelength 300～390nm scope, down with) makes this curing of coating, forms the tunicle of thickness 1.2 μ m by cured article, obtains the sample 1 that substrate surface has the tunicle of cured article formation.
[example 2～11]
Mixture in example 1 (A), colloid silica (B) and solvent types and consumption become the kind and amount of following table 2 record, other and example 1 identical acquisition sample 2～11.
According to method shown below the various rerum naturas of said sample 1～11 are measured and estimated, the results are shown in table 2.
[static resistance] is for the initial stage sample with through the sample of (after preserving 500 hours in 80 ℃, the atmosphere of humidity 90%) after the humidity test, method according to JIS K1049 regulation, after the high-voltage (10kV) that sample is applied certain hour makes it charged, measure with voltage weakening to 1/2 o'clock required time.Measure and adopt シ シ De static Co., Ltd. special formula electrostatic tester in system Nice difficult to understand.
The state of [outward appearance after the humidity test] and initial stage sample is made comparisons, and no albefaction, is designated as " zero " when apparent variation such as oozing out, peeling off.
[transparency] calculates its mean value with the turbidity value (%) in the place, 4 place on the turbidometer mensuration sample.
[wear resistant] according to the abrasion resistance test method among the ISO 9352, respectively in the weight of 2 CS-10F wearing and tearing load on the wheel 500g, measures turbidity when its rotation 500 is changeed with turbidometer.Carry out in the place, 4 place of the circular trackway that is determined at abrasion wheels of turbidity, measures mean value.Wear resistant is with value (%) expression of (turbidity after the wear test)-(initial stage turbidity) gained.
[surface lubrication] measures the kinetic friction coefficient on the surface of sample in accordance with the following methods for the initial stage sample with through the sample of (after preserving 500 hours in 80 ℃, the atmosphere of humidity 90%) after the humidity test.Under following condition, measure the weight (g) that moves horizontally the required slide plate that bears a heavy burden, (the required weight/heavy burden) of trying to achieve is kinetic friction coefficient.
Test pad: Mierocrystalline cellulose system non-woven fabrics (Asahi Kasei Corporation's system, trade(brand)name " ベ Application コ Star ト ")
Bear a heavy burden: 500g (contact area 50mm * 100mm)
Miles of relative movement: 20mm
Translational speed: 10mm/ minute
Testing circumstance: 25 ℃, relative humidity 45%.
[anti-fingerprint tack] for the initial stage sample with through the sample of (after preserving 500 hours in 80 ℃, the atmosphere of humidity 90%) after the humidity test, as the yardstick of anti-fingerprint tack, measures sample and oleic contact angle as one of human body sebum composition.There are the high more surface of anti-fingerprint tack itself and the big more tendency of oleic contact angle.
Use automatic contact angle determination meter (DSA10D02 Germany Network Le ス corporate system), on syringe needle, forms the oleic drop of 3 μ L, it is contacted, the formation drop with specimen surface in drying regime (20 ℃, relative humidity 65%).Contact angle is meant the tangent line of fluid surface on the point that solid contacts with liquid and the angle that solid surface forms, to comprise the viewpoint definition of liquid.
The ratio of the multipolymer (A1) in the mixture of example 7 (A) is too small, and static resistance is poor.The ratio of the multipolymer (A1) in the mixture of example 8 (A) is excessive, and wear resistant is poor, oozing out of multipolymer (A1) occur at specimen surface after the humidity test.The ratio of the monomeric unit with quaternary ammonium salt group in the multipolymer of example 9 (A1) is too small, and static resistance is poor.The ratio of the monomeric unit with quaternary ammonium salt group in the multipolymer of example 10 (A1) is excessive, and the transparency is poor.Do not have remaining hydroxyl in the multipolymer of example 11 (A1), static resistance is poor.
The possibility of utilizing on the industry
The formed products that substrate surface has a tunicle that the solidfied material by active energy ray curable coating composition of the present invention forms is applicable to display or as surface-coated dose of use of CD.
Claims (9)
1. active energy ray curable coating composition; it is characterized in that; the mixture (A) and the colloid silica (B) that comprise compound with (methyl) acryl; 22～62% hydroxyls for the isocyanate group that makes the compound (c) that contains (methyl) acryl and isocyanate group in 1 molecule and polymkeric substance (b) of mixture (A) have carried out the multipolymer (A1) of the structure that addition reaction gets; described polymkeric substance (b) is by comprising the free radical polymerization monomer (a1) with quaternary ammonium salt group; have the free radical polymerization monomer (a2) of hydroxyl and have 1 expression of following formula structure free radical polymerization monomer (a3) free radical polymerization monomer mixture (a) reaction and get; the ratio of monomer (a1) is 20～45 mass parts with respect to total 100 mass parts of monomer mixture (a) and compound (c); 20～85 moles of % of the hydroxyl in the monomer mixture (a) and the isocyanic ester radical reaction of compound (c)
-(C (=O) C
mH
2mO)
n-... formula 1
In the formula 1, m is 3～5 integer, and n is 1～10 integer.
2. active energy ray curable coating composition as claimed in claim 1 is characterized in that, the ratio of monomer (a1) is 23～40 mass parts with respect to total 100 mass parts of monomer mixture (a) and compound (c).
3. active energy ray curable coating composition as claimed in claim 1 is characterized in that, 30～80 moles of % of the hydroxyl in the monomer mixture (a) and the isocyanic ester radical reaction of compound (c).
4. active energy ray curable coating composition as claimed in claim 1 is characterized in that, 40～75 moles of % of the hydroxyl in the monomer mixture (a) and the isocyanic ester radical reaction of compound (c).
5. active energy ray curable coating composition as claimed in claim 1; it is characterized in that; the mixture (A) that has the compound of (methyl) acryl with respect to 100 mass parts, the conduct that comprises 0.1～500 mass parts forms the colloid silica (B) of branch admittedly.
6. active energy ray curable coating composition as claimed in claim 1; it is characterized in that; have (methyl) acryl compound mixture (A) 0.01～10% be intramolecularly has position (α) that at least 1 part by the part that is selected from following formula 2～6 expression forms, the position (β) that formed by at least 1 part of the part that is selected from following formula 7～9 expressions reaches (methyl) acryl compound (A2)
-(SiR
1R
2O)
p-... formula 2
-(CF
2CF
2O)
q-... formula 3
-(CF
2CF (CF
3) O)
r-... formula 4
-(CF
2CF
2CF
2O)
s-... formula 5
-(CF
2O)
t-... formula 6
In the formula 2, R
1, R
2Represent in the fluorine-containing alkyl or phenyl of alkyl, carbonatoms 1～8 of carbonatoms 1～8 any independently, p is 1～1000 integer, and in the formula 3～6, q, r, s and t are respectively 1～100 integer,
-R
3-... formula 7
-(CH
2CH
2O)
x-(CH
2CH (CH
3) O)
y-... formula 8
-(C (=O) C
uH
2uO)
z-... formula 9
In the formula 7, R
3Be the alkylidene group of carbonatoms 6～20, in the formula 8, x and y are 0～100 the integer that satisfies 5≤x+y≤100, and in the formula 9, u is 3～5 integer, and z is 1～20 integer.
7. coating composition as claimed in claim 6 is characterized in that, aforesaid compound (A2) represented by any formula in the following formula,
R
5(SiR
1R
2O)
p-SiR
1R
2CH
2CH
2CH
2O-B-(CH
2CH
2O)
X-(CH
2CH(CH
3)O)
Y-A
R
5(SiR
1R
2O)
p-SiR
1R
2CH
2CH
2CH
2O-B-(C(＝O)C
UH
2UO)
Z-A
In the following formula, A:-CONH-CH
2CH
2OCOC (R
4)=CH
2, B: singly-bound ,-CH
2CH
2O-,-CONH-C
6H
4-CH
2-C
6H
4-NHCOO-,-CONH-CH
2CH
2CH
2CH
2CH
2CH
2-NHCOO-,-CONH-C
6H
3(CH
3)-NHCOO-,-CONH-C
10H
6-NHCOO-,-CO-C
6H
4-COO-,-CO-C
iH
2i+1-COO-, wherein i is 0～10 integer, R
4: hydrogen atom or methyl, R
5: the alkyl that can contain the carbonatoms 1～8 of etheric oxygen atom.
8. coating composition as claimed in claim 6 is characterized in that, aforesaid compound (A2) represented by any formula in the following formula,
R
fO-(CF
2CF
2O)
q-CF
2CH
2O-B-(CH
2CH
2O)
X-(CH
2CH(CH
3)O)
Y-A
R
fO-(CF
2CF
2O)
q-CF
2CH
2O-B-(C(＝O)C
UH
2UO)
Z-A
R
fO-(CF
2CF
2O)
q-(CF
2O)
t-CF
2CH
2O-B-(CH
2CH
2O)
X-(CH
2CH(CH
3)O)
Y-A
R
fO-(CF
2CF
2O)
q-(CF
2O)
t-CF
2CH
2O-B-(C(＝O)C
UH
2UO)
Z-A
R
fO-(CF(CF
3)CF
2O)
r-CF(CF
3)CH
2O-B-(CH
2CH
2O)
X-(CH
2CH(CH
3)O)
Y-A
R
fO-(CF(CF
3)CF
2O)
r-CF(CF
3)CH
2O-B-(C(＝O)C
UH
2UO)
Z-A
R
fO-(CF
2CF
2CF
2O)
s-CF
2CF
2CH
2O-B-(CH
2CH
2O)
X-(CH
2CH(CH
3)O)
Y-A
R
fO-(CF
2CF
2CF
2O)
s-CF
2CF
2CH
2O-B-(C(＝O)C
UH
2UO)
Z-A
In the following formula, A:-CONH-CH
2CH
2OCOC (R
4)=CH
2, B: singly-bound ,-CH
2CH
2O-,
-CONH-C
6H
4-CH
2-C
6H
4-NHCOO-、-CONH-CH
2CH
2CH
2CH
2CH
2CH
2-NHCOO-、
-CONH-C
6H
3(CH
3)-NHCOO-、-CONH-C
10H
6-NHCOO-、-CO-C
6H
4-COO-、
-CO-C
iH
2i+1-COO-, wherein i is 0～10 integer, R
4: hydrogen atom or methyl, R
f: can contain etheric oxygen atom carbonatoms 1～16 contain fluoroalkyl ,-(CF
2CF
2O)-unit and-(CF
2O)-unitary arrangement mode can be that block-wise also can be random shape.
9. molding is characterized in that, the thickness that has the cured article formation of each described coating composition in the claim 1～8 on substrate surface is the tunicle of 0.1～50 μ m.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP091995/2004 | 2004-03-26 | ||
| JP2004091995 | 2004-03-26 | ||
| PCT/JP2005/005435 WO2005092991A1 (en) | 2004-03-26 | 2005-03-24 | Active energy ray-curable coating composition and molding thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1934201A CN1934201A (en) | 2007-03-21 |
| CN1934201B true CN1934201B (en) | 2011-04-13 |
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|---|---|
| US (1) | US7514479B2 (en) |
| JP (1) | JPWO2005092991A1 (en) |
| KR (1) | KR20060131902A (en) |
| CN (1) | CN1934201B (en) |
| TW (1) | TW200609313A (en) |
| WO (1) | WO2005092991A1 (en) |
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| JP4992356B2 (en) * | 2006-09-14 | 2012-08-08 | 大日本印刷株式会社 | Antistatic photocurable resin composition, and antistatic film and article using the same |
| US8614286B2 (en) * | 2008-09-02 | 2013-12-24 | Ppg Industries Ohio, Inc. | Biomass derived radiation curable liquid coatings |
| JP4277936B1 (en) * | 2008-12-05 | 2009-06-10 | 東洋インキ製造株式会社 | Active energy ray curable composition |
| EP2401337B1 (en) * | 2009-02-27 | 2018-05-09 | PPG Industries Ohio, Inc. | Biomass derived radiation curable liquid coatings |
| GB0919014D0 (en) | 2009-10-30 | 2009-12-16 | 3M Innovative Properties Co | Soll and stain resistant coating composition for finished leather substrates |
| EP2412739A1 (en) * | 2010-07-27 | 2012-02-01 | Cytec Surface Specialties, S.A. | Radiation curable aqueous compositions |
| TWI593739B (en) * | 2013-02-04 | 2017-08-01 | Arakawa Chemical Industries Ltd | An active energy ray-curable resin composition, an active energy ray-curable resin composition, a cured film and an antistatic transparent optical film |
| JP6582485B2 (en) * | 2015-03-27 | 2019-10-02 | セイコーエプソン株式会社 | Composition, method for producing shaped article, and shaped article |
| US10544260B2 (en) | 2017-08-30 | 2020-01-28 | Ppg Industries Ohio, Inc. | Fluoropolymers, methods of preparing fluoropolymers, and coating compositions containing fluoropolymers |
| TWI737949B (en) * | 2017-12-22 | 2021-09-01 | 日商荒川化學工業股份有限公司 | Antistatic agent for active energy ray curable resin composition, active energy ray curable resin composition, cured product and film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002173516A (en) * | 2000-12-05 | 2002-06-21 | Mitsubishi Chemicals Corp | Actinic energy ray-curable aqueous emulsion composition |
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| JPH0611767B2 (en) * | 1985-02-06 | 1994-02-16 | 出光石油化学株式会社 | Photocurable composition |
| JP3068284B2 (en) * | 1991-10-04 | 2000-07-24 | 帝人株式会社 | Antistatic synthetic resin molded product |
| JPH06311563A (en) * | 1993-04-23 | 1994-11-04 | Toshiba Corp | Remote control system |
| JPH0772721A (en) * | 1993-06-29 | 1995-03-17 | Mitsubishi Chem Corp | Conductive controlling member |
| JP3837811B2 (en) * | 1996-07-16 | 2006-10-25 | 旭硝子株式会社 | UV-curable coating composition |
| JP3888485B2 (en) * | 1997-06-27 | 2007-03-07 | 大日本インキ化学工業株式会社 | UV curable composition |
| US6383641B1 (en) * | 1997-08-15 | 2002-05-07 | Asahi Glass Company Ltd. | Transparent coated molded product and method for producing the same |
| KR100322578B1 (en) * | 1998-10-02 | 2002-03-08 | 윤종용 | Data communication device and method between WAP terminal and WAP server |
| JP4089121B2 (en) * | 2000-03-21 | 2008-05-28 | 三菱化学株式会社 | Antistatic agent |
| JP4401049B2 (en) * | 2000-12-11 | 2010-01-20 | 旭硝子株式会社 | Curable composition, cured coating and coated substrate |
| JP2002194250A (en) * | 2000-12-27 | 2002-07-10 | Mitsubishi Chemicals Corp | Active energy ray-curable coating composition and material having cured coating film of the same |
| JP3676260B2 (en) * | 2000-12-28 | 2005-07-27 | ナトコ株式会社 | Active energy ray curable urethane (meth) acrylate, active energy ray curable composition and use thereof |
| WO2003002628A1 (en) * | 2001-06-27 | 2003-01-09 | Daikin Industries, Ltd. | Surface-treating agent composition and process for producing the same |
| JP4456827B2 (en) * | 2002-05-22 | 2010-04-28 | 共栄社化学株式会社 | Antistatic coating agent composition |
| JP4750342B2 (en) * | 2002-07-03 | 2011-08-17 | ルネサスエレクトロニクス株式会社 | MOS-FET, manufacturing method thereof, and semiconductor device |
| JP2004095410A (en) * | 2002-08-30 | 2004-03-25 | Tocad Energy Co Ltd | Part alignment structure in battery pack |
| JP2004263144A (en) * | 2003-03-04 | 2004-09-24 | Asahi Glass Co Ltd | Sebum smudging resistant coating composition and coated molded product with cured material layer of the same |
| JP2005230709A (en) * | 2004-02-20 | 2005-09-02 | Mm System:Kk | Treatment system for polluted water |
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| JP2002173516A (en) * | 2000-12-05 | 2002-06-21 | Mitsubishi Chemicals Corp | Actinic energy ray-curable aqueous emulsion composition |
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| US7514479B2 (en) | 2009-04-07 |
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